Herbicidal 3-(substituted ureido)crotonamides

ABSTRACT

This invention relates to herbicidal methods, compounds and compositions utilizing as an essential ingredient a compound of the following formula: WHEREIN R is phenyl or o-fluorophenyl, and X is methyl or halogen. Typical of the compounds of this invention is 2-bromo-N(phenylcarbamoyl)-3-(3-phenylureido)crotonamide which is useful as an herbicide.

United States Patent 91 Loux [ HERBICIDAL 3-(SUBSTITUTEDUREIDO)CROTONAMIDES =[75] Inventor: Harvey M. Loux, Hockessin, Del.

[73] Assignee: E. I. du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: March 4, 1971 [21] Appl. No.: 121,145

Related US. Application Data [52] US. Cl ..71/120, 260/553 A [51] Int.Cl. ..A01n 9/20 [58] Field of Search ..7l/l06, 120

[56] References Cited UNITED STATES PATENTS 3,228,972 l/l966 Schwartz..71/106 X [111 3,719,467 51 March 6, 1973 11/1966 Ellis ..71/106 2/1966Loux ..7l/93X Primary ExaminerJames 0. Thomas, Jr. Attorney-Don M. Kerr7 ABSTRACT This invention relates to herbicidal methods, compounds andcompositions utilizing as an essential ingredient a compound of thefollowing formula:

HIX

wherein R is phenyl or o-fluorophenyl, and X is methyl or halogen.

Typical of the compounds of this invention is 2-bromo-N-(phenylcarbamoyl )-3-( 3 -phenylureido)crotonamide which isuseful as an herbicide.

7 Claims, No Drawings HERBICIDAL 3-(SUBST1TUTED stituents are asfollows:

UREIDO)CROTONAMIDES R is phenyl, and

X is chlorine, bromine or methyl.

CROSS REFERENCE To RELATED These compounds are preferred in that manyhave APPLICATIONS 5 substantial herbicidal activity at lowconcentrations. This application is a continuation-in-part applicationThose compound? whch are Preferred havmg directed to subject matterdivided from my-copending the best usecost are the followmgi applicationSet. No. 882,343, filed Dec. 4, 1969 now -P Y! -P US. Pat. No.3,664,823, that is a continuation-in-part )cmmnam'de of my copendingapplication Ser. No. 775,568, filed l l Sept. 30, 1968, that is acontinuation-inpart of my then reldmcmmnamlde copending application Ser.No. 678,548, filed Oct. 27, PREPARATION [967, that was acontinuation-in-part of my then copertding application Ser. No. 533,223,filed Mar. 10, Illustrative of the general preparation of the crotona-1966 all now abandoned. mides of the invention is the following reactionscheme:

O X a X BACKGROUND OF THE INVENTION X is methyl or halogen as above. Thd l t f w as f h rbicidal om A substituted urea is reacted with ana-s'ubstituted p g zgz i lgx 5:?) 235 acetoacetic acid ester in thepresence of a small i d f h t l t th a 35 amount of an acid catalystsuch as p-toluenesulfonic gzgz a g gg fi r j z gg -igfip g l b g acid orsulfuric acidin an inert water-immiscible solvent s ch as benzen ortoluene. Water i l' d Pat. No. 3,235,357 which it has been discoveredalso u e S e [Inmate h h l during the condensation. This water isremoved from ave er ac the reaction site as quickly as possible, as forexample SUMMARY OF THE INVENTION 40 by az'eotro'p'ic distillation.

The reaction mix is cooled and stripped free of solvent under reducedpressure yielding a mixture of products. This mixture is generally ofsufficient purity to be formulated directly as a herbicidal compositionwithout further purification. The technical materials obtained above mayhowever be recrystallized from a variety of solvents such as ethanol,acetonitrile, water r and cyclohexane. Alternatively, the reactionmixture is H cooled and filtered if necessary. The solid, a mixture ofR-NHcNHwG.=(|J-'o-NHCNH starting urea and 1,3-disubstituted urea, isdiscarded.

H, x Alternatively, the reaction mixture can be extracted with sodiumhydroxide solution, which yields, on

acidification with a suitable acid, the crotonamide,

This invention relates to crotonamides having herbicidal activity,compositions einploying these compounds and methods for using them asherbicides.

The compounds of this invention are illustrated by 5 the followingformula:

wherein Y which may be recrystallized from a solvent, such as R isselected from the group consisting of phenyl or acetonitrile.

o-fluorophenyl, and I When X is a chlorine, bromine or iodine atom, the

X is methyl or halogen. compounds may also be made by synthesizing theun- Preferred compounds because of their outstanding substitutedcrotonamide first and then halogenating it herbicidal activity andeconomy of preparation are with a suitable reagent such as sulfurylchloride, N- those compounds of the formula wherein thesubbromosuccinimide, bromine,or iodine and nitric acid.

The compounds used in this invention are useful for controlling thegrowth of many unwanted weeds and vegetation. Examples of some of theweeds and vegetation which may be controlled with the compounds used inthis invention are the following:

crabgrass Digitaria .rpp. goosegrass Eleusinz indica white cloverTrifolium repens broomsedge Andropogon virginicus povertygrassSporabolus vagr'mifloms dune sandspur Cenchrus spp. carpetweed Moll'ugoverlict'llala common chickweed Sullaria media mouseear chickweedCerasuum vulgalum purslane Portulaca oleracea downy brome Bromuslectorum the foxtails Selaria .rpp.

fall panicum Panicum dicholomalflorum annual morningglory lpomoea .rpp.

lambsquarters Chenopodium album ragweed Ambrosia .rpp.

mustard Bmssica .rpp.

quackgrass Agrapyron repens smooth bromegrass Bramus inermis nutsedgeCyperus spp.

wild carrot Daucus camta cheatgrass- Bromus secalinus peppergrass-Lepidium spp.

wild oats Avena farua poison ivy- Rhus radicans witchgrass Panic-umcapillare birch Betula spp.

box elder Acer negundo willow Salix spp.

oaks Quercus spp.

in accordance with the present invention, these crotonamides hereof havebeen found useful for controlling the growth of unwanted vegetation.When applied at rates of l: to 50 KgJhectare, they control many speciesof herbaceous and woody plants. As will be obvious to those skilled inthe art, the preferred rate depends on the time and method ofapplication and the species to be controlled. In general, the lowerrates are used in crops to control annual weeds and the higher rates forcontrol of perennial or established annual vegetation in non-crop land.

COMPOSITIONS The herbicidal compounds defined herein may normally beincorporated with various materials to prepare compositions suitable forapplication by conventional agricultural equipment. Suitablecompositions of the present invention can be prepared by admixing atleast one of the active components with pest control adjuvants ormodifiers to provide solid or liquid compositions inthe form of dusts,granules, pellets, waterdispersible and water-soluble powders,high-strength concentrates, aqueous dispersions or emulsions andsolutions or dispersions inorganic liquids. Suitable solid carriers arenatural clays such as kaolinite, attapulgite and montmorillonite. lnadditiomtalcs, pyrophillite, diatomaceous silica, synthetic finesilicas, calcium aluminosilicates, sodium aluminosilicates andtricalcium phosphate are suitable solid carriers. Organic materialssuchas walnut shell flour, wood flour or redwood bark flour may also be usedas a suitable solid carrier. The percentages by weight of the essentialactive ingredient will vary with the manner in which the composition isto be applied. The content of active component may be as low as 0.5percent when applied as a dust or as high as percent when used as a spottreatment in small isolated areas.

Liquid herbicidal compositions consist, for example, of the activecompounds homogeneously dispersed in water or other non-solvent mediumsuch as a substantially aliphatic hydrocarbon oil. Since certain of theactive compounds of this invention are water-soluble in the presence ofalkali, liquid compositions may also be true solutions in water ifcombined with a strong base such as sodium hydroxide or sodiummetasilicate. Oil solutions may also be prepared with solvents such asaromatic hydrocarbons, chlorinated hydrocarbons, esters and ketones. Inorder to secure homogeneous dispersions in non-solvent media, surfaceactive agents are used. in fact, preferred herbicidal compositions ofthis invention whether liquid or solid contain the active componenthomogeneously admixed with one or more surfactants as well as carriers.These surface active agents are those commonly known as wetting agents,dispersing agents and emulsifying agents. They may act as wetting agentsfor wettable powders, pellets, granules, high strength concentrates anddusts, as dispersing agents for wettable powders and suspensions and asemulsifying agents for emulsifiable concentrates. Surfactants may alsoenhance the biological activity of the compounds of this invention. Suchsurface active agents can include anionic, cationic and nonionicsubstances.

In general, less than 10 percent by weight of the surface-active agentwill be used in compositions of this invention and ordinarily the amountof surface-active agents will range from 1-5 percent but may even beless than 1 percent by weight.

Additional surface-active agents can be added to the formulations toincrease the ratio of surfactantzactive ingredient up to as high as 5zlby weight. Such compositions have a greater herbicidal effectivenessthan can be expected from a consideration of the activity of thecomponents used separately. When used at higher rates it is preferredthat the surfactant'be present in the range of one-fifth to five partssurfactant for each one part of active agent. I

A comprehensive list of such agents may be found in Detergents andEmulsifiers, 1967 Annual" by John W. McCutcheon. A few dispersants ofnonionic type such as low-viscosity methylcellulose, low-viscositypolyvinylalcohol and acacia gum are not listed in the above Annual buthave also been found to be suitable.

Suitable surface active agents for use in compositions of this inventioninclude polyethylene glycol esters with fatty acids and rosin acids,polyethylene glycol ethers with alkylated phenols or with long-chainaliphatic alcohols, polyethylene glycol ethers with sorbitan fatty acidesters, and polyoxyethylene thioethers. Still other suitable surfactantsinclude amine, alkali and alkaline earth salts of alkylaryl sulfonicacids, amine, alkali and alkaline earth fatty alcohol sulfates, dialkylesters of alkali metal sulfosuccinates, fatty acid esters of amine,alkali and alkaline earth isethionates and taurates, amine, alkali andalkaline earth salts of lignin sulfonic acids, hydroxyethylatedcellulose, amine, alkali and alkaline earth salts of polymerizedalkylnaphthalene sulfonic acids, and long-chain quarternary ammoniumcompounds. Anionic and nonionic surface active agents are preferred.

Among preferred wetting agents are sodium alkylnaphthalene sulfonates,sodium dioctylsulfosuccinate, sodium dodecylbenzene sulfonate, ethyleneoxide condensates with alkylated phenols such as octyl, nonyl, ordodecylphenol, sodium lauryl sulfate, and trimethylnonyl polyethyleneglycol.

Among preferred dispersing agents are sodium, calcium, and magnesiumlignin sulfonates, low viscosity methyl cellulose, polymerized sodiumalkylnaphthalene sulfonate, sodium N-oleyl or N-lauryl isethionates,sodium N-methyl-N-oleyl taurate, sodium dodecyldiphenyloxidedisulfonate, and polyethylene oxide adducts .to mixed fatty and rosinacids. A preferred dispersant for oil suspensions is soya lecithin.

Among preferred emulsifying agents are ethylene oxide adducts tosorbitan esters of lauric, oleic, stearic,- or palmitic acid,polyethylene glycol esters with lauric, oleic, stearic, palmitic, orrosin acids, oil-soluble alkylaryl sulfonates, oil-solublepolyoxyethylene ethers with octyl-, nonyl-, and dodecylphenol,polyoxyethylene adducts to long-chain mercaptans, and mixtures of thesesurfactants.

Compositions of the herbicidal crotonamides with inert solid diluentsare ordinarily prepared in two forms; as wettablepowders or dusts withfinely divided diluents and as granules or pellets with agglomeratedforms of the diluent. When the composition is a wettable powder, amixture of the active ingredient, inert diluent, wetting agent,dispersing agent and optionally corrosion inhibitor and/or anti-foamingagent is intimately blended and ground until substantially all particlesare below 50 microns. The content of active component may vary from20-95 percent but 50-80 percent is generally preferred.

Thus, wettable powder formulations of the invention will contain fromabout 20 to 95 weight per cent active material, from 0.5 to 2.0 weightper cent wetting agent, from 0.25 to 5.0 weight per cent dispersant, andfrom 4.25 to 79.25 percent weight per cent inert extender, as theseterms are described above.

When the wettable powder contains a corrosion inhibitor or ananti-foaming agent or both, the corrosion inhibitor will not exceedabout 1 per cent of the composition, and the anti-foaming agent will notexceed about 0.5 per cent by weight of the composition, both replacingequivalentamounts of the inert extender.

Dusts are dense powder compositions which are intended for applicationin dry form, in accordance with the preferred compositions and methodsof the invention. Dusts are characterized by their free-flowing andrapid settling properties so that they are not readily windborne toareas where their presence is not desired. They contain primarily anactive material and a dense, free-flowing, solid extender.

Their performance is sometimes aided by the inclusion of a wettingagent, and convenience in manufacture frequently demands the inclusionof an inert, absorptive grinding aid. For the dust compositions of thisinvention, the inert extender may be either of vegetable or mineralorigin, the wetting agent is preferably anionic or non-ionic, andsuitable absorptive grinding. aids are of mineral origin.

Suitable classes of inert solid extenders for use in the dustcompositions are those organic or inorganic powders which possess highbulk density and are very freeflowing. They are also characterized bypossessing relatively low surface areas and are poor in liquidabsorption. Suitable classes of grinding aids are natural clays,diatomaceous earths, and synthetic mineral fillers derived from silicaor silicate. Among ionic and nonionic wetting agents, the most suitableare the members of the group known to the art as wetting agents andemulsifiers. Although solid agents are preferred because of ease inincorporation some liquid non-ionic agents are also suitable in the dustformulations.

Preferred inert solid extenders for the dusts of this invention aremicaceous tales, pyrophyllite, dense kaolin clays, tobacco dust andground calcium phosphate rock such as that known as Phosphodust", atrademark of the American Agricultural Chemical Company.

Preferred grinding aids are attapulgite clay, diatomaceous silica,synthetic fine silica and synthetic calcium and magnesium silicates.Preferred wetting agents are those previously described under wettablepowder formulations.

The inert solid extenders in the dusts of this invention are usuallypresent in concentrations of from about 30 to weight per cent of thetotal composition. The grinding aid will usually constitute 5 to 50weight per cent of the composition, and the wetting agent willconstitute from about 0 to 1.0 weight per cent of the composition. Dustcompositions can also contain other surfactants such as dispersingagents in concentrations of up to about 0.5 weight per cent.

The wettable powders described above can also be used in the preparationof dusts. While such wettable powders could be used directly in dustform, it is more advantageous to dilute them by blending with the densedust diluent. In this manner, dispersing agents, corrosion inhibitors,and anti-foam agents may also be found as components of a dust.

Thus, the dust compositions of this invention will comprise about 5 to20 weight per cent active material, 5 to 50 weight per cent absorptivefiller, 0 to 1.0 weight per cent wetting agent, and about 30 to 90weight per cent dense, free-flowing dust diluent, as these terms areused herein. Such dust formulations can contain, in addition, minoramounts of dispersants, corrosion inhibitors, and anti-foam agents,derived from the wettable powders used to make the dusts.

Granules and pellets are physically stable, particulate compositionscontaining an active compound which adheres to or is distributed througha basic matrix of a coherent, inert carrier with macroscopic dimensions.In order to aid leaching of the active ingredient from the granule orpellet, a surfactant can be present. I

For the compounds of this invention, the inert carrier is preferably ofmineral origin.

Suitable carriers are natural clays, some pyrophyllites and vermiculite.Suitable wetting agents are anionic or non-ionic.

For the granule compositions of this invention, most suitable carriersare of two types. The first are porous, absorptive, preformed granules,such as preformed and screened granular attapulgite or heat expanded,granular, screened vermiculite. On either of these, a solution orsuspension of the active agent can be sprayed and will be absorbed oradsorbed at concentrations up to 25 weight per cent of the total weight.The second, which are also suitable for pellets, are initially powderedkaolin clays, hydrated attapulgite, or bentonite clays in the form ofsodium, calcium or magnesium bentonites. Water-soluble salts, such assodium salts, may also be present to aid in the disintegration ofgranules or pellets in the presence of moisture. These ingredients areblended with the active components to give mixtures that are granulatedor pelleted, followed by drying, to yield formulations with the activecomponent distributed uniformly throughout the mass. Such granules andpellets can also be made with 25 to 30 weight per cent active component,but more frequently a concentration of about It) weight per cent isdesired for optimum distribution. The granular compositions of thisinvention are most useful in a size range of 15 60 mesh.

The most suitable wetting agents for the granular compositions of thisinvention depend upon the type of granule used. When preformed granulesare sprayed with active material in liquid form the most suitablewetting agents are non-ionic, liquid wetters miscible with the solvent.These are compounds more generally known to the art as emulsifiers, andcomprise alkylaryl polyether alcohols, alkyl polyether alcohols,polyoxyethylene sorbitan fatty acid esters, polyethylene glycol esterswith fatty or rosin acids, fatty alkylol amide condensates, oil solublepetroleum or vegetable oil sulfonates, or mixtures of these. Such agentswill usually comprise up to about 5 weight per cent of the totalcomposition.

When the active ingredient is first mixed with a powdered carrier andsubsequently granulated, or pelleted, liquid non-ionic wetters can stillbe used, but it is usually preferable to incorporate at the mixing stageone of the solid, powdered anionic wetting agents such as thosepreviously listed for the wettable powders. Such agents will comprisefrom about to 2 weight per cent of the total composition.

Thus, the preferred granular or pelleted formulations of this inventioncomprise about 5 to 30 weight per cent active material, about 0 to 5weight per cent wetting agent, and about 65 to 95 weight per cent inertmineral carrier, as these terms are used herein.

High-strength compositions generally consist of 90 to 99.5 percentactive ingredient and 0.5 to percent of a liquid .or solid surfactant.Small amounts of conditioning agents may also be included, replacing anequal weight of surfactant. Such high-strength compositions can often beused in a manner similar to the wettable powders but they are alsosuitable for further formulation.

The aqueous suspension concentrates are prepared by mixing together andsandgrinding an aqueous slurry of water-insoluble active ingredient inthe presence of dispersing agents. Thus, there is obtained aconcentrated slurry of very finely divided particles in which the activeingredient is substantially all below 5 microns in size. Thisconcentrated aqueous suspension is characterized by its extremely smallparticle size so that upon diluting and spraying, a very uniformcoverage is obtained.

These aqueous suspension concentrates will contain from l5 to 40 percentof active ingredient, from 45 to 70 percent water with the remaindermade up of surfactants, corrosion inhibitors, and suspending agents.

Suspensions in organic liquids can be prepared in a similar manner suchas by replacing the water with mineral oil.

Emulsifiable oils are usually solutions of active material innon-water-miscible solvents together with a surfactant.

For the compounds of this invention, emulsifiable oils can be made bymixing the active ingredient with a solvent and surfactant. Suitablesolvents for the compounds of this invention are aromatic hydrocarbonsincluding many weed oils, chlorinated solvents, and nonwater-miscibleethers, esters, or ketones. Suitable surfactants are those anionic ornon-ionic agents known to the art as emulsifying agents.

Emulsifying agents most suitable for the emulsifiable oilcompositions ofthis invention are long-chain alkyl or mercaptan polyethoxy alcohols,alkylaryl polyethoxy alcohols, sorbitan fatty acid esters,polyoxyethylene ethers with sorbitan fatty acid esters, polyethyleneglycol esters with fatty or rosin acids, fatty alkylol amidecondensates, calcium and amine salts of fatty alcohol sulfates, oilsoluble petroleum sulfonates or, preferably, mixtures of theseemulsifying agents. Such emulsifying agents will comprise from about 1to 10 weight per cent of the total composition. As described above,however, up to 5 parts of emulsifying agent for each part of activecompound can be used. 1

Thus, emulsifiable oil compositions of the present invention willconsist of from about 15 to 50 weight per cent active material, about 40to 82 weight per cent solvent, and about 1 to 10 weight per centemulsifier, as these terms are defined and used above.

in some instances the oil solution may be intended merely for extensionwith other oils, such as weed oils. In this instance, the emulsifyingagents may be omitted and may be replaced by additional solvent.

Water-soluble formulations can be prepared by combining certaincompounds of this invention with alkaline solubilizing agents such asalkali metal hydroxide, silicates, phosphates and carbonates. Suchcompositions will consist of 20-80 percent active compound, 5-40 percentof alkali metal hydroxide, phosphate or silicate and 15-40 percent ofalkali metal carbonate.

APPLICATION The compounds used in this invention are generally appliedto a locus to be protected from undesirable vegetation. The locus to beprotected is the soil. It may be barren of vegetation at the time thecompounds are applied or vegetation may have begun to appear or be evenfully developed. The locus to be protected also includes the surface ofvarious weeds whose destruction is desired. Undesired vegetation can beany plants which are generally classified as weeds or for that matterany plant which is growing in an area in which the plant is not desired.

The herbicidally effective amount of a compound used in this inventionwhich will control undesired vegetation depends on climatic conditionsand soil type. The exact quantity required will be apparent to oneskilled in the art. Generally, the compounds used in this invention areapplied to sandy soils at rates of 2 to 60 kilograms per hectare, andthe preferred rate is in the range of 5 to 40 kilograms per hectare. Itwas noted that the compounds of the invention are most advantageouslyapplied to the soil in the early spring before the new growth ofvegetation begins.

The following examples illustrate the preparation, formulation andapplication of the herbicidal compounds of the invention. All parts andpercentages are by weight unless otherwise indicated.

PREPARATION Example I A mixture of 11 parts of phenylurea, 5.9 parts ofethyl Z-methylacetoacetate, 0.5 parts of p-toluenesulfonic acid, and 90parts of benzene is refluxed for 4 days with stirring and continuousremoval of water by means of a suitable condenser trap. Six-tenths partsof water is collected. The mixture is filtered. About 2 parts of1,3-diphenylurea is obtained. One-half of the solution is stripped ofsolvent under reduced pressure and the remaining cake is dried andpulverized.

The other half of the benzene solution is extracted with 100 parts ofpercent sodium hydroxide solution and the latter is acidified withconcentrated hydrochloric acid. The resulting precipitate is collectedon a filter and washed thoroughly with water.Z-Methyl-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide is obtained.

In an analogous manner the following compounds are made:

2-methyl-N-( phenylcarbamoyl )-3-[ 3-(o-fluorophenyl)-ureido]crotonamide2-fluoro-N-(phenylcarbamoyl)-3-(3-phenylureido)- crotonamide Example 112-bromo-N-(phenylcarbamoyl)-3-( 3-phenylureido)- crotonamide Ten partsdiketene is slowly added to a solution of 13.6 parts of phenyl urea and3.0 parts of mercuric acetate in 80 parts of glacial acetic acid. Thissolution is allowed to mix at room temperature for 5 hours, thenfiltered to l 1 1 parts of N-(phenylcarbamoyl)acetoacetamide, m.p.146-147C.

A mixture of l 1.1 parts of the above acetoacetamide and 6.8 parts ofphenyl urea and 1.0 parts of ptoluenesulfonic acid is then trap refluxedin 264 parts of benzene until the theoretical amount of water iscollected (0.9 parts). The mixture is then cooled and filtered to 15.8parts of N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide, m.p.l88191C.

To a mixture of 15.8 parts of the above crotonamide in 284 parts ofglacial acetic acid is added 5.1 parts of sodium acetate. To thismixture is added a solution of 7.0 parts bromine in 30 parts of glacialacetic acid and the combination stirred at room temperature for 16hours, then filtered to 12.6 parts of crude material which isrecrystallized from ethyl acetate to 2-bromo-N-(phenylcarbamoyl)-3-(3-phenyl-ureido)crotonamide, m.p. 160-162C.

2-Bromo-N-(phenylcarbamoyl)-3-[3-(o-fluorophenyl)-ureido]crotonamide isprepared in an analogous fashion.

Example 111 2-chloro-N-(phenylcarbamoyl)-3-(3-phenylureido)- crotonamideThree parts of N-phenylcarbamoyl-3-(3-phenylureido)-crotonamide isslurried up in ml. of xylene at 65C. 1.2 parts of sulfuryl chloride in10 ml. of xylene is added drop-wise over a 10-min. period. The mixtureis stirred at 65C. for 30 minutes, cooled, and extracted with aqueoussodium hydroxide solution. The alkaline solution is acidified withhydrochloric acid, and the precipitate filtered off and washedthoroughly with water and air-dried, yielding2-chloro-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide of sufficientpurity for herbicidal application.

An alternate synthesis for the above crotonamide is as follows:

To 74.3 parts of N-(phenylcarbamoyl)acetoacetamide slurried in 962 partsof methylene chloride at 10C. is added 49.9 parts of sulfuryl chloride.The mixture is left at room temperature 19 hours, then filtered to 38.9parts of 2-chloro-N-(phenylcarbamoyl)acetoacetamide, m.p. l38-141.5C.

A mixture of 4.9 parts of above acetoacetamide and 2.7 parts of phenylurea and 0.4 parts of p-toluene sulfonic acid is trap refluxed in 88parts of benzene until the theoretical amount of water is collected(0.36 parts). The mixture is cooled and filtered to 6.2 parts of2-chloro-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide, m.p.173-176C.

2-Chloro-N-(phenylcarbamoyl)-3-[3 (o-fluorophenyl)-ureido]crotonamide isprepared in a fashion similar to the above syntheses. 1

Example IV 2-iodo-N-(phenylcarbamoyl)-3-(3-phenylureido)- crotonamide3.4 parts of N-(phenylcarbamoyl)-3-(3-phenylureido )-crotonamide and 1.3parts of iodine is dissolved in 25 ml. of glacial acetic acid. Thesolution is heated to 45C. and 1.1 part of fuming nitric acid added.vThe reaction mixture is stirred at'room temperature for 1 hour andpoured onto an ice-water mixture. The product is filtered andrecrystallized from an ethanolwater mixture. v

Example V Percent Z-methyl-N-(phenylcarbamoyl)-3-(3-phenyl-ureido)crotonamide 80 Alkyl naphthalene sulfonic acid, Na salt 2Partially desulfonated sodium lignin sulfonate 2 Diatomaceous silica 4Kaolin clay 12 The above components are blended and micropulverizeduntil substantially all particles are less than 50 microns.

The following compounds can be formulated in like manner:

2-chloro-N-(phenylcarbamoyl)-3-( 3-phenylureido crotonamide2-bromo-N-(phenylcarbamoyl)-3-(3-phenylureido)- crotonamide2-iodo-N-(phenylcarbamoyl)-3-(3-phenylureido)- Fuel oil No. 2

crotonamide 2-fluoro-N-( phenylcarbamoyl )-3-( 3-phenylureido)crotonamide2-methyl-N-(phenylcarbamoyl)-3-[3-(o-fluorophenyl)-ureido]crotonamideExample Vl Percent 2-methyl-N-(phenylcarbamoyl)-3 3-phenyl-ureido)crotonamide 25 Anhydrous sodium metasilicate 37 Anhydrouspotassium carbonate 37.5 Sodium dioctylsulfosuccinate 0.5

The above components are blended, micropulverized and reblended. Uponaddition to water, the strongly alkaline environment solubilizes theactive compound and a homogenous solution is formed.

The active component in the above formulation may be replaced by thefollowing crotonamide:

2-methyl-N-(phenylcarbamoyl)-3-(phenylureido)- crotonamide.

Example Vll Percent 2-methyl-N-(phenylcarbamoyl)-3-[3-ofluorophenyhureidolcrotonamide 30 Ca, Mg Ligninsulfonate l5 Hydrated attapulgite 1.8 Sodium carbonate anhydrous 2.5Sodium pentachlorophenate 0.7

WAter 5 Example VllI Percent Z-bromo-N phenylcarbamoyl)-3-( 3-phenyl-ureido )crotonamide 25 Soya lecithin 5 The above components areblended, then sand ground or pebble milled until substantially allparticles are less than 5 microns. The resulting oil dispersion may bediluted with herbicidal oils to a proper use level.

Example IX Percent 2-methyl-N-(phenyicarbamoyll-3-(3-phenyhureido)crotonlmide 25 Anhydrous sodium sulfate to Non-swelling Ca,Mg. bentonite 64 Alkyl naphthalene sulfonic acid, Ne 1 salt The activecomponent, the sodium sulfate and the surfactant are first blended andmicropulverized, then blended with bentonite and moistened with [5 to 19percent water. A uniform paste is obtained by pug milling. The resultingpaste is extruded through ris inch die holes, fitted with cutting knivesthat form pellets is X ,4: inch, which are subsequently dried.

The active component above may be replaced by any of the crotonamidesdisclosed in this invention to yield a similar formulation.

Example X Percent Z-bromo-N-(phenylcarbamoyl)-3-(3- phenyl-ureido)crotonamide l0 Propylene glycol 10 Granular vermiculite (Zonolite No.4)

The active component is first micropulverized to a line powder, thenblended briefly with the vermiculite. The propylene glycol is thensprayed rapidly upon the tumbling mix to prevent segregation in storageand handling.

Any of the crotonamides disclosed in this invention may be substitutedfor the active named component above to yield a similar granularformulation.

Example Xl Percent 2-methy|-N-( phenylcarbamoyl )-3 3- phenyl-ureido)crotonamide 12.5 Micaceous talc. 87.5

The above components are mixed together in a ribbon blender to produce a10 percent active dust which is applicable to areas where the hazard ofdrift to desirable vegetation is not a problem.

Example XII Percent 2-methyl-N-(phenylcarbarnoyl)-3-(3-phenyl-ureido)crotonarnide 25 Diesel oil 67 Blend of oil soluble aminesalt of dodecylbenzene sulfonic acid and ethylene oxide modified fattyester of sorbitol 8 The above composition is sand or pebble milled untilmost particles are less than 5 microns. When added to water, the oildispersion emulsifies. The active particles for the most part remainwithin the dispersed oil phase but there is some distribution betweenphases to yield solid particles dispersed in water and solid particlesdispersed in an emulsified oil phase.

Example XIll Percent 2-bromo-N-(phenylcarbamoyl)-3-(3-phenyl-ureido)crotonamide 9 Finely divided synthetic silica 5. 3.Trimethylnonyl polyethylene glycol ether 2.

COO

The above ingredients are coarsely ground to pass a 0.42 millimeterscreen. This high-strength composition can be applied directly or usedfor further formulation.

The following series of examples illustrate the methods of employing theabove formulations to control undesired vegetation.

Example XIV The formulation of Example V using any of the six listedactive ingredients is extended with water in such a manner that a rateof 50 pounds active ingredient per acre is applied in 100 gallons ofwater to weed infested areas along power line rights-of-way. Thetreatment results in kill of annual and perennial weeds such asplantain, crabgrass, horsenettle, foxtail, and panic grass. Woody plantssuch as willow, alder, and sumac are controlled.

Example XV Sixty pounds of the formulation of Example VI is applied in100 gallons of water along railroad rights-ofway. The treatment resultsin control of unwanted vegetation such as toad flax, barnyardgrass,ragweed, goosegrass, crabgrass, wild mustard and seedling Johnson grass.

Example XVI Example XVII The formulation of Example VIl is diluted withoil so that 25 pounds per acre (active ingredient) are applied in 80gallons of herbicidal oil to vegetation growing around oil tank farms orgrain elevators. The application results in control of annual andperennial vegetation.

Example XVIII The pellets formed in Example IX are scattered byhelicopter over a stand of arborvitae at a rate of 8 pounds (activeingredient) per acre. Treatment is made early in the spring before weedsemerge. The treatment results in kill of crabgrass, foxtail, mustard,ragweed,

and barnyardgrass while allowing conifers to grow normally.

Example XIX The granules of Example IX are spread with a fertilizerspreader in late summer at a rate of 8 pounds (active ingredient) peracre on an area which is to be planted with young Christmas trees thefollowing spring. The application is made on rows 18 inches widecoinciding with the rows to be planted to trees. The treatment resultsin control of weeds under the small seedlings for the next summer andallows easier maintenance of the young tree.

Example XX Thirty-two pounds per acre of the dust of Example XI areapplied with a grain drill before final harrowing to a cultivated fieldwhich is to be held fallow for one season. The final harrowingdistributes the material so that extended control is obtained of suchspecies as ragweed, mustard, flower-of-an-hour, crabgrass, foxtail andcheatgrass.

Example XXI The formulation of Example XII is extended with water insuch a manner that 1% pound per acre (active ingredient) is applied in20 gallons of water as a direct post emergence spray to a newly plantedfield of sugarcane at the time of the last cultivation. The treatmentresults in control of the weeds growing in the row and providespreemergence control of weeds for four to six weeks. The cane showsnormal growth.

I claim:

1. A method for the control of undesired vegetation, comprising applyingto the locus to be protected a herbicidally effective amount of acompound of the formula:

wherein R is phenyl or o-fluorophenyl, and

X is methyl or halogen.

2. A method for the control of undesired vegetation comprising applyingto the locus to be protected a'herbicidally effective amount of acompound as described in claim 1 wherein R is phenyl; and

X is chlorine, bromine or methyl.

3. A method according to claim 2 wherein the compound is2-chloro-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide.

4. A method according to claim 2 wherein the compound is2-bromo-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide.

5. A herbicidal composition comprising an inert diluent and aherbicidally effective amount of a compound of the following formula:

HaX

wherein R is phenyl or o-fluorophenyl, and

X is methyl or halogen.

6. A herbicidal composition comprising an inert diluent and aherbicidally effective amount of a compound as described in claim 5wherein R is phenyl; and

X is chlorine, bromine or methyl.

7. A herbicidal composition comprising an inert diluent and aherbicidally effective amount of a compound as described in claim 5wherein R is phenyl; and

X is chlorine, bromine, or methyl.

-. A method for the control of undesired vegetation, comprising applyingto the locus to be protected a herbicidally effective amount of acompound of the formula: wherein R is phenyl or o-fluorophenyl, and X ismethyl or halogen.
 2. A method for the control of undesired vegetationcomprising applying to the locus to be protected a herbicidallyeffective amount of a compound as described in claim 1 wherein R isphenyl; and X is chlorine, bromine or methyl.
 3. A method according toclaim 2 wherein the compound is2-chloro-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide.
 4. A methodaccording to claim 2 wherein the compound is2-bromo-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide.
 5. Aherbicidal composition comprising an inert diluent and a herbicidallyeffective amount of a compound of the following formula: wherein R isphenyl or o-fluorophenyl, and X is methyl or halogen.
 6. A herbicidalcomposition comprising an inert diluent and a herbicidally effectiveamount of a compound as described in claim 5 wherein R is phenyl; and Xis chlorine, bromine or methyl.